EP3242909B1 - Thermoplastische folien mit asymmetrischen eigenschaften und verfahren - Google Patents

Thermoplastische folien mit asymmetrischen eigenschaften und verfahren Download PDF

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Publication number
EP3242909B1
EP3242909B1 EP16735364.8A EP16735364A EP3242909B1 EP 3242909 B1 EP3242909 B1 EP 3242909B1 EP 16735364 A EP16735364 A EP 16735364A EP 3242909 B1 EP3242909 B1 EP 3242909B1
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European Patent Office
Prior art keywords
film
polyethylene terephthalate
layer
stretching
multilayer film
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English (en)
French (fr)
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EP3242909A1 (de
EP3242909A4 (de
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Steve SARGEANT
Sudhir Naik
J.K. Sharma
Pramod Sirsamkar
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Flex Films (USA) Inc
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Flex Films (USA) Inc
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Publication of EP3242909A4 publication Critical patent/EP3242909A4/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
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    • B29D7/01—Films or sheets
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes

Definitions

  • the presently-disclosed subject matter relates to films having asymmetric properties and processes for producing the same.
  • the presently-disclosed subject matter relates to thermoplastic, biaxially-oriented polyethylene terephthalate films that have a tear force in the longitudinal direction that is about 1.5 times as large as a tear force in the transverse direction.
  • Thermoplastic films are known in the art and can be manufactured from semicrystalline resins such as polyethylene terephthalate (PET), polyethylene, cycloolefin copolymers, ethylene vinyl alcohol copolymers, nylons, polylactic acids, polypropylene, polyphenylene sulphate, and other materials.
  • PET polyethylene terephthalate
  • cycloolefin copolymers polyethylene vinyl alcohol copolymers
  • nylons polylactic acids
  • polypropylene polypropylene
  • polyphenylene sulphate polyphenylene sulphate
  • a number of thin polymer films can be prepared commercially with processes that involve sequential melting, extrusion, and solidification of the polymer material into a thin cross-section. Orientation of such polymer films through blowing or mechanical methods in the longitudinal (machine) and transverse directions can significantly increase the crystallinity of the films, which can, in turn, affect tear, twist, optical, and other mechanical properties of films.
  • the amorphous content of any PET film is the weight fraction of material that is not crystallized within the biaxial orientation process, and that the densification of the amorphous phase implies that the mass per unit volume of non-crystalline material is increased (see, e.g., Polymer Bulletin, April 1988, Volume 19, Issue 4, pp. 397-401 ).
  • the semicrystalline nature of oriented polymer films implies a weight fraction of such film is crystalline, whereas the remaining portion of the material is amorphous.
  • the ratio of crystalline to amorphous domains is strongly influential for properties like gas barrier properties, thermal resistance, density, optical clarity, and other commercially-valuable properties.
  • oriented polymer films including PET films
  • the nodular structure and small isometric crystallites within biaxially-oriented PET film may contribute to PET film ductility at low temperatures (see Klement and Geil, Journal of Macromolecular Science, Part B: Physics Volume 5, Issue 3, 1971 ).
  • Such morphological attributes can be introduced and controlled through process conditions including stretching ratios, speed of stretching, temperature of stretching, crystallization temperatures, and the like.
  • thermoplastic materials with good twist or tear properties have involved making such films at relatively low orientation ratios.
  • construction of low stretch ratio films can be problematic due to the likelihood of high shrinkage during subsequent use of the films as well as poor commercial runability of the films. Such shrinkage would be further exacerbated as temperatures increased.
  • thermoplastic PET film with easy twist and tear properties without the requirement of using low molecular weight additives or low stretch ratios to construct the material.
  • Such films and processes would be desirable and beneficial for a range of commercial applications including, but not limited to, the packaging of food, candy, novelties, and other commodities.
  • KR2014012022A discloses a biaxially elongated multi-layered polyester matter film which has a three-layered structure.
  • US2015/004387A1 discloses a high-barrier film that includes a biaxially-oriented polyethylene terephthalate layer.
  • the presently-disclosed subject matter includes thermoplastic polyethylene terephthalate films and processes for producing the same.
  • the presently-disclosed subject matter includes thermoplastic polyethylene terephthalate films having a biaxially-oriented polyethylene terephthalate layer, a tensile strength in the longitudinal direction of about 2000 kg/cm 2 or more, a tensile strength in the transverse direction of about 3000 kg/cm 2 or more, and a tear force in the longitudinal direction that is about 1.5 times as large as a tear force in the transverse direction.
  • the polyethylene terephthalate used for the films can be selected from a polyethylene terephthalate homopolymer, a polyethylene terephthalate copolymer, and a combination thereof.
  • the PET layer included in the films of the presently-disclosed subject matter is generally prepared by processes known to those of ordinary skill in the art including the use of conventional sequential biaxial orientation machines having a single screw mainline extrusion train and a twin screw sub-extrusion process.
  • standard PET pellets having a desired intrinsic viscosity can be fed into the main extrusion line, while a blend of standard PET pellets and PET pellets having a different composition (e.g., PET pellets including an inorganic additive) can be fed in to the sub-extrusion process, such that the materials can be melted separately and then laminated together in a feed-block to produce a desired molten structure (e.g., an A/B/A molten structure) in an extrusion die.
  • the laminated PET material or layer emerging from the extrusion die can then be quenched on a chilled casting drum to produce a thick, amorphous film structure.
  • the PET layer is then preferably stretched about 2 to about 5 times in the machine, or longitudinal, direction and, after the acrylic primer coating process described below, about 2 to about 5 times in the transverse direction, followed by heat crystallization.
  • a layer of PET material is obtained having a tensile strength of at least about 2000 kg/cm 2 (2 Pa) or 3000 kg/cm 2 (3 Pa) in both the transverse and the longitudinal direction of the film, and having dimensions that are about 2 to about 4.5 times those originally found in the PET layer in both the longitudinal and transverse direction.
  • the resulting PET layer has a total thickness of about 6 ⁇ m to about 9 ⁇ m.
  • Some embodiments of the presently-described films are multilayer films that comprise two or more layers, and in some instances include three layers. Some embodiments of the multilayer films comprise one or more layers that include silica. In some embodiments, silica is added to a layer, such that the resulting film has a dynamic coefficient of friction (COF) to steel of less than about 0.45 ⁇ D, or, in some embodiments, of less than about 0.45 ⁇ D to steel when heated to 150 °C. In some embodiments, silica is added to one or more layers comprised of polyethylene terephthalate to thereby form a polyethylene terephthalate-silica layer, which can be formed, for example, in the sub-extrusion process described herein.
  • COF dynamic coefficient of friction
  • the films have a three-layer "A/B/A" structure that includes, from top to bottom, a first polyethylene terephthalate layer, a polyethylene terephthalate-silica layer, and a second polyethylene terephthalate layer.
  • the films have a total thickness of about 50 ⁇ m or less. In some embodiments, the films have a total thickness of about 30 ⁇ m or less. In some embodiments, the films have a total thickness of about 5 ⁇ m to about 15 ⁇ m.
  • thermoplastic film with asymmetric properties processes for producing a thermoplastic film with asymmetric properties.
  • a process for producing a thermoplastic film is provided wherein a biaxially-oriented polyethylene terephthalate layer is first produced by melting an amount of polyethylene terephthalate pellets to form an initial polyethylene terephthalate layer.
  • a biaxially-oriented polyethylene terephthalate layer that includes silica is produced by melting together an amount of polyethylene terephthalate pellets and silica.
  • the polyethylene terephthalate layer can then be laminated on to one or both sides of the polyethylene terephthalate layer that includes silica, the co-extruded layer, to thereby produce a multilayer film.
  • the multilayer film is first stretched in a longitudinal direction, and then the multilayer film is stretched in a transverse direction.
  • the step of stretching the multilayer film in the longitudinal direction includes, in some embodiments, stretching the multilayer film by a factor of about 2 to about 4.
  • the step of stretching the multilayer film in the transverse direction includes, in some embodiments, stretching the multilayer film by a factor of about 3 to about 4.5.
  • the step of stretching the multilayer film in the transverse direction is performed at a temperature of about 80 °C to about 140 °C.
  • coating the multilayer film comprises inline coating the multilayer film.
  • the presently-disclosed subject matter includes films having asymmetric properties as well as processes for producing the same.
  • the presently-disclosed subject matter includes, in some embodiments, thermoplastic, biaxially-oriented polyethylene terephthalate (PET) films that have a tear force in the longitudinal (machine) direction that is about 1.5 times as large as a tear force in the transverse direction.
  • PET polyethylene terephthalate
  • thermoplastic film comprises a biaxially-oriented polyethylene terephthalate layer having asymmetric properties.
  • thermoplastic is used herein to refer to a material that generally is capable of being repeatedly hardened when cooled and softened when heated.
  • the films are characterized in both a longitudinal direction, or the direction that the film moves in during the manufacturing process, and in a transverse direction, which is perpendicular to the longitudinal direction.
  • the thermoplastic films comprise a tensile strength in the longitudinal direction of about 2000 kg/cm 2 (2 Pa) or more, including about 2000 kg/cm 2 (2 Pa) to about 10,000 kg/cm 2 (10 Pa). In some embodiments, the thermoplastic films further comprise a tensile strength in the transverse direction of about 3000 kg/cm 2 (3 Pa) or more, including about 3000 kg/cm 2 (3 Pa) to about 10,000 kg/cm 2 (10 Pa).
  • the polyethylene terephthalate layer included in the thermoplastic films comprises polyethylene terephthalate homopolymers, where the polyethylene terephthalate layer consists of only polyethylene terephthalate.
  • other embodiments of the present thermoplastic films include a polyethylene terephthalate layer that comprises polyethylene terephthalate copolymers, wherein the polyethylene terephthalate layer includes polyethylene terephthalate and one or more additional co-monomers.
  • Additional co-monomers that can be used in this regard include, but are not limited to, diethylene glycol, propylene glycol, neopentyl glycol and polyalkylene glycols, 1,4-butane diol, 1,3-propane diol, and dicarboxylic acids such as adipic acid, sebacic acid, malonic acid, succinic acid, isophthalic acid, and 2,6-napthalenedicarboxylic acid.
  • diethylene glycol propylene glycol
  • neopentyl glycol and polyalkylene glycols 1,4-butane diol
  • 1,3-propane diol 1,3-propane diol
  • dicarboxylic acids such as adipic acid, sebacic acid, malonic acid, succinic acid, isophthalic acid, and 2,6-napthalenedicarboxylic acid.
  • the polyethylene terephthalate layer included in the films of the presently-disclosed subject matter is generally prepared by processes known to those of ordinary skill in the art including the use of conventional sequential biaxial orientation machines having a single screw mainline extrusion train and a twin screw sub-extrusion process.
  • standard polyethylene terephthalate pellets having a desired intrinsic viscosity can be fed into the main extrusion line, while pellets of another composition can be fed into a sub-extrusion process.
  • a blend of standard polyethylene terephthalate pellets and silica-filled polyethylene terephthalate pellets can be fed in to the sub-extrusion process.
  • the materials can then be melted separately and laminated together in a feed-block to produce a desired multilayer molten structure (e.g., an A/B/A molten structure) in an extrusion die.
  • the thermoplastic films described herein can thus be comprised of a plurality of layers or in other words can comprise a "multilayer film" having two or more layers that can differ in composition and/or physical properties.
  • the thermoplastic films comprise three layers (e.g., an A/B/A configuration).
  • at least one of the layers in an exemplary multilayer film includes silica.
  • exemplary multilayer films comprise a layer that includes silica interposed between layers that do not include silica.
  • the multilayer film comprises, from top to bottom, a first polyethylene terephthalate layer, a polyethylene terephthalate-silica layer, and a second polyethylene terephthalate layer.
  • the laminated polyethylene terephthalate material or layer emerging from the extrusion die is generally subsequently quenched on a chilled casting drum to produce a thick, amorphous film structure.
  • the thermoplastic film is then stretched about 2 to about 5 times in the longitudinal direction.
  • the step of stretching the multilayer film in the longitudinal direction includes stretching the multilayer film by a factor of about 2 to about 4.
  • the film is then stretched about 2 to about 5 times in the transverse direction.
  • the step of stretching the multilayer film in the transverse direction includes stretching the multilayer film by a factor of about 3 to about 4.5.
  • the thickness of the resulting films can depend on a variety of factors, including, but not limited to, the number of layers in the film, the thickness of the individual layers, the stretching ratio, and the like. In some embodiments, by stretching the resulting film in the above-described manner, the film has a total thickness of about 100 ⁇ m or less, a total thickness of about 70 ⁇ m or less, a total thickness of about 50 ⁇ m or less, a total thickness of about 30 ⁇ m or less, or a total thickness of about 10 ⁇ m or less.
  • the film has a total thickness of about 5 ⁇ m to about 50 ⁇ m, including about 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, and 50 ⁇ m.
  • stretching in the transverse direction is performed at a temperature of about 80 °C to about 140 °C, including, in some embodiments, about 70 °C, about 80 °C, about 90 °C, about 100 °C, about 110 °C, about 120 °C, about 130 °C, and about 140 °C.
  • the presently-disclosed subject matter provides thermoplastic films and processes for producing the same that utilize the orientation of the thermoplastic films as well as other parameters to tune the tear properties of the films.
  • the resulting thermoplastic film includes a tear force in the longitudinal direction that differs from the tear force in the transverse direction.
  • tear force refers to the force required to move a tear through a material in a particular direction, but that excludes the force required to initiate a tear in a material, or to completely separate a material into two respective pieces.
  • the thermoplastic films comprise a tear force in the longitudinal direction that is about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8, about 1.9, about 2.0, about 2.1, about 2.3, about 2.4, or about 2.5 times as large as a tear force in the longitudinal direction.
  • the thermoplastic films comprise a tear force in the longitudinal direction that is about 1.5 times as large as a tear force in the longitudinal direction.
  • one or more materials can also be added to one or more of the layers of the thermoplastic film to produce a thermoplastic film or layer thereof having a desired dynamic coefficient of friction.
  • dynamic coefficient of friction refers to the coefficient of friction which persists during a sliding motion at a given speed. The coefficient of friction is determined as the ratio of the frictional force to the normal force, acting perpendicular to the two surfaces in contact. Methods for determining coefficients of friction can be found, for example, in International Organization for Standardization Standard ISO 8295 for Plastics Film and Sheeting, Determination of the Coefficients of Friction.
  • silica is added to a polyethylene terephthalate layer to achieve a desired dynamic coefficient of friction (COF) for a resulting film.
  • a PET film is provided that includes a dynamic COF of about 0.45 ⁇ D or less, 0.35 ⁇ D or less, 0.25 ⁇ D or less, or 0.15 ⁇ D or less.
  • a film is provided that is configured to include a particular dynamic COF to steel when heated to 150 °C, including, in some embodiments, a dynamic COF of about 0.45 ⁇ D or less, 0.35 ⁇ D or less, 0.25 ⁇ D or less, or 0.15 ⁇ D or less.
  • a coating is also applied to the film to impart one or more additional properties onto the film.
  • a coating can be applied to the film after the step of stretching the multilayer film in a longitudinal direction, but prior to the step of stretching the multilayer film in the transverse direction.
  • the step of coating the film comprises coating at least one side of the film with a coating selected from the group consisting of an acrylic coating, a polyurethane coating, a polysulphonester coating, and a quaternary ammonium-based coating.
  • the step of coating the film comprises coating the film with an acrylic primer, which, in certain embodiments, can then form a cross-linked acrylic primer layer on the film.
  • an acrylic primer layer is typically highly cross-linked and capable of providing a relatively low dynamic COF to metal to increase the contact of film to metal.
  • the dynamic COF of the acrylic layer of the film to the metal is about 0.15 ⁇ D to about 0.45 ⁇ D when heated to 150 °C.
  • the dynamic COF of the acrylic layer of the film to the metal is about 0.15 ⁇ D, about 0.20 ⁇ D, about 0.25 ⁇ D, about 0.30 ⁇ D, about 0.35 ⁇ D, about 0.40 ⁇ D, or about 0.45 ⁇ D.
  • the dynamic COF of the acrylic layer of the film to the metal is less than about 0.45 ⁇ D when heated to 150 °C. In some embodiments, the dynamic COF of the acrylic layer of the film to the metal is less than about 0.20 ⁇ D when heated to 150 °C.
  • the acrylic primer layer can be comprised of an acrylic resin that adheres well to a polyethylene terephthalate layer.
  • acrylic resins can be selected from resins having a monomer component such as, for example, an alkyl acrylate, an alkyl methacrylate, (examples of such alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, a lauryl group, a stearyl group, a cyclohexyl group, a phenyl group, a benzyl group, a phenylethyl group and the like), a monomer having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
  • the acrylic primer is comprised of a copolymer of methyl methacrylate that further includes methacrylic acid and methacrylonitrile.
  • the acrylic primer is comprised of a co-polymer of methylmethacrylate, butylacrylate, methacrylic acid, methyl acrylate, acrylic acid, and hydroxyethylmethacrylate, alone or in combination with other monomers, as such a combination of monomers has been observed to produce an acrylic primer layer having sufficient hardness and COF values as well as a sufficient ability to adhere to down-stream sealants including, but not limited to, polyethylene, ethylene vinyl acetate, ethylene methyl acrylate, and copolymers and terpolymers thereof.
  • one or more cross-linking agents can also be included in the acrylic primer layer to harden the acrylic primer layer, to reinforce the bonding between the various layers of the thermoplastic film, and to also provide a highly cross-linked layer capable of providing increased thermal resistance.
  • cross-linking agents that can be used with the acrylic components include, but are not limited to, melamine-based cross-linkers, epoxy-based cross-linkers, aziridine-based cross-linkers, epoxyamide compounds, titanate-based coupling agents (e.g., titanium chelate), oxazoline-based cross-linkers, isocyanate-based cross-linkers, methylolurea or alkylolurea-based cross-linkers, aldehyde-based cross-linkers, and acrylamide-based cross-linkers.
  • the cross-linking agent is selected from melamine, epoxy-based cross-linkers, and aldehyde-based cross-linkers.
  • the cross-linking agents are included in the acrylic primer layer to produce a cross-linked acrylic primer layer having a cross-linking density of about 10%, about 15%, about 20%, about 25%, about 30%, or about 40%. In some embodiments, the cross-linking agents are included in the acrylic primer layer to produce a cross-linked acrylic primer layer having a cross-linking density of greater than about 10%.
  • the acrylic primer layer can be applied to the film by a number of methods, including application of the acrylic primer in a dispersion or solution of water, and by an application method such as gravure coating, meyer rod coating, slot die, knife over roll, or any variation of roll coating.
  • the acrylic primer layer is applied by inline coating, whereby the acrylic primer layer is applied to the film as it is being produced. More specifically, and as described above, the acrylic primer layer can be applied to both sides of the film by inline coating immediately after stretching the film in the longitudinal direction.
  • the thickness of the acrylic primer layer that is applied to at least one side of the film is about 0.3 ⁇ m, about 0.25 ⁇ m, about 0.2 ⁇ m, about 0.15 ⁇ m, about 0.10 ⁇ m, or about 0.05 ⁇ m.
  • Example 1 Thermoplastic polyethylene terephthalate (PET) film
  • a polyethylene terephthalate film was prepared in a conventional sequential biaxial orientation machine.
  • the machine consisted of a single screw mainline extrusion train and a twin screw sub extrusion process. Briefly, polyethylene terephthalate pellets of an intrinsic viscosity (IV) of 0.62 were fed into the main extrusion train at a rate of 650 Kg/hr. Into the sub-extrusion process, a blend of 0.62 IV polyethylene terephthalate pellets (75%) and silica filled polyethylene terephthalate pellets (25%) were fed into the system. The amount of silica used was optimized to produce a COF of less than 0.45 ⁇ D at the end of the film making process. These materials were then separately melted and laminated together in a feed-block to produce an A/B/A molten structure in the extrusion die.
  • IV intrinsic viscosity
  • the molten laminated polyethylene terephthalate material that emerged from the extrusion die was subsequently quenched on a chilled casting drum to produce a thick, amorphous film structure. Subsequently, this film was stretched in the longitudinal, or machine or lengthwise, direction through a heated roller assembly. The ratio of this stretching was varied. After longitudinal stretching, the film was then stretched in the transverse direction.
  • the film was stretched in the longitudinal direction by a factor of 3.5.
  • the film was then attached to a chain rail and entered a tenter for transverse orientation by a factor of about 4.1.
  • the temperature at which the transverse orientation was performed varied from standard procedures, and Table 1 shows the temperatures of the transverse orientation at different locations.
  • Table 1 Transverse Orientation Temperatures at Various Locations Location Temp.
  • the resulting film had a thickness of about 12 ⁇ m. Additionally, the films included a tensile strength in the longitudinal and transverse directions of about 2000 kg/cm 2 and 3000 kg/cm 2 , respectively and, in some instances, higher tensile strength values.
  • a control film was prepared for comparison to the film described in Example 1. Using the procedures described in Example 1, a polyethylene terephthalate layer was laminated on both sides of a polyethylene terephthalate-silica layer to produce an A/B/A molten structure in the extrusion die.
  • the molten laminated polyethylene terephthalate material was subsequently quenched on a chilled casting drum, and then the control film was stretched in longitudinal direction through a heated roller assembly by a factor of 3.4. Next, without coating the film, the film was side-ways drawn at a stretch ratio of approximately 4.0 in the transverse direction.
  • the temperature at which the transverse orientation was performed varied, and Table 2 shows the temperatures of the transverse orientation at different locations.
  • the resulting film was about 12 ⁇ m thick.
  • This Example describes a process for analyzing the longitudinal and transverse tear properties of the films produced in Examples 1 and 2.
  • both sets of films were provided, and 2 inch (5 cm) x 5 inch (13 cm) samples of the films were cut in both the longitudinal direction and the transverse directions.
  • Five samples were cut in each direction and for each film, which produced a total of 20 samples.
  • each of the samples were then cut 3.5 inches (8.9 cm) from the center of one of the 2 inch (5 cm) sides, leaving a 1.5 inch (3.8 cm) tail from the other end of the sample that was still attached.
  • an Instron Tensile Tester (Instron, Norwood, MA) was provided, and was configured such that it would record and report total work and displacement for each trial.
  • the Tensile Tester was also configured such that it registered a "break” and stopped recording once the tear reached the edge of the respective samples.
  • the samples were inserted into the Tensile Tester so that the tear was oriented vertically. Specifically, one free end of the sample where the tear had initiated was attached to the top clamp, then, while applying light tension, the other free end of the sample where the tear had initiated was attached to the bottom clamp. As shown in FIG. 2B , the remaining 1.5" long tail portion of the sample was kept straight and perpendicular to the direction of the tear. Without being bound by theory or mechanism, keeping the tail portion straight and horizontal avoided force magnification, and the sample was also held so as to avoid pulling on the upper "leg" when inserting the sample into the Tensile Tester.
  • control film exhibited tear properties in the transverse direction that were similar to the tear properties in the longitudinal direction.
  • the tear properties of the control film in both the transverse direction and longitudinal direction were also found to be similar to a similar commercially-obtained biaxially-oriented PET film that, like the control film, exhibited significantly different properties when compared to the PET film of the present invention having asymmetric tear properties (Table 4) .
  • Table 4 Sample Orientation Tear Force 1 Tear Force 2 Tear Force 3 Average (Newton) Control 1 LD 0.079 0.066 0.063 0.069 Control 1 TD 0.084 0.080 0.054 0.062

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Claims (13)

  1. Thermoplastische Folie, die Folgendes umfasst:
    eine biaxial orientierte Polyethylenterephthalat(PET)-Schicht;
    eine Zugfestigkeit in der Längsrichtung von etwa 2000 kg/cm2 (2 Pa) oder mehr;
    eine Zugfestigkeit in der Querrichtung von etwa 3000 kg/cm2 (3 Pa) oder mehr; und
    eine Reißkraft in der Längsrichtung, die etwa 1,5-mal so groß ist wie eine Reißkraft in der Querrichtung,
    wobei die Folie zwei oder mehr Schichten umfasst.
  2. Folie nach Anspruch 1, wobei die Polyethylenterephthalatschicht ein Polyethylenterephthalat-Homopolymer, ein Polyethylenterephthalat-Copolymer oder eine Kombination davon umfasst.
  3. Folie nach Anspruch 1, die ferner eine Beschichtung auf wenigstens einer Seite der Folie umfasst, wobei die Beschichtung aus der Gruppe ausgewählt ist, die aus einer Acrylbeschichtung, einer Polyurethanbeschichtung, einer Polysulfonesterbeschichtung und einer Beschichtung auf quaternärer Ammoniumbasis besteht.
  4. Folie nach Anspruch 1, wobei die Folie im Wesentlichen aus drei Schichten besteht und/oder wobei eine oder mehrere der Schichten Siliciumdioxid beinhalten, wobei die eine oder die mehreren Schichten, die Siliciumdioxid beinhalten, optional einen dynamischen Reibungskoeffizienten zu Stahl von etwa 0,45 µD oder weniger aufweisen, wie etwa wobei die eine oder die mehreren Schichten, die Siliciumdioxid beinhalten, einen dynamischen Reibungskoeffizienten zu Stahl von etwa 0,45 µD oder weniger aufweisen, wenn diese auf 150 °C erhitzt werden.
  5. Folie nach Anspruch 4, wobei die Schicht, die Siliciumdioxid beinhaltet, aus Polyethylenterephthalat besteht.
  6. Folie nach Anspruch 4, wobei die Schicht, die Siliciumdioxid beinhaltet, zwischen Schichten eingefügt ist, die kein Siliciumdioxid beinhalten.
  7. Folie nach Anspruch 4, wobei die Folie von oben nach unten eine erste Polyethylenterephthalatschicht, eine Polyethylenterephthalatsiliciumdioxidschicht und eine zweite Polyethylenterephthalatschicht umfasst.
  8. Folie nach Anspruch 1, wobei die Folie eine Gesamtdicke von etwa 50 µm oder weniger aufweist, wie etwa wobei die Folie eine Gesamtdicke von etwa 30 µm oder weniger aufweist, wie etwa wobei die Folie eine Gesamtdicke von etwa 5 µm bis etwa 15 µm aufweist.
  9. Vorgang zum Herstellen der thermoplastischen Folie nach Anspruch 1, der Folgendes umfasst:
    Herstellen einer biaxial orientierten Polyethylenterephthalat(PET)-Schicht;
    Herstellen einer biaxial orientierten Polyethylenterephthalatschicht, die Siliciumdioxid (PET-Siliciumdioxid) beinhaltet;
    Laminieren der Polyethylenterephthalatschicht auf einer oder beiden Seiten der Polyethylenterephthalatsiliciumdioxidschicht, um eine Mehrschichtfolie herzustellen;
    Strecken der Mehrschichtfolie in einer Längsrichtung; und
    Strecken der Mehrschichtfolie in einer Querrichtung bei einer Temperatur, die niedriger als bei dem Strecken in der Längsrichtung ist,
    wobei das Verfahren ferner das Beschichten wenigstens einer Seite der Mehrschichtfolie nach dem Schritt des Streckens der Mehrschichtfolie in einer Längsrichtung und vor dem Schritt des Streckens der Mehrschichtfolie in der Querrichtung umfasst.
  10. Vorgang nach Anspruch 9, wobei der Schritt des Streckens der Mehrschichtfolie in der Längsrichtung das Strecken der Mehrschichtfolie um einen Faktor von etwa 2 bis etwa 4 beinhaltet.
  11. Vorgang nach Anspruch 9, wobei der Schritt des Streckens der Mehrschichtfolie in der Querrichtung das Strecken der Mehrschichtfolie um einen Faktor von etwa 3 bis etwa 4,5 beinhaltet.
  12. Vorgang nach Anspruch 9, wobei der Schritt des Streckens der Mehrschichtfolie in der Querrichtung bei einer Temperatur von etwa 80 °C bis etwa 140 °C durchgeführt wird.
  13. Vorgang nach Anspruch 9, wobei das Beschichten der Mehrschichtfolie das Inline-Beschichten der Mehrschichtfolie umfasst.
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US10662311B2 (en) 2020-05-26
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